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      Hydrophilic-Lipophilic-Difference (HLD) Guided Formulation of Oil Spill Dispersants with Biobased Surfactants Translated title: Hydrophil-Lipophil-Differenz (HLD)-gesteuerte Formulierung von Ölkatastrophen-Dispergiermitteln mit biobasierten Tensiden

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          Abstract

          The large-scale use of dispersants during the BP Horizon spill revealed various risks associated with these formulations, particularly the use of volatile organic compound (VOC) solvents linked to respiratory illnesses, and the poor biodegradability of surfactants. Previous attempts at solving these issues involved formulations of lecithin and polyethylene glycol ester of sorbitan monooleate (Tween ® 80) that still required the use of a volatile solvent, ethanol. In this work, the Hydrophilic-Lipophilic Difference (HLD) framework was used to develop a lecithin formulation containing food-grade lipophilic (Glycerol MonoOleate – GMO- and sorbitan monooleate – Span ® 80) and hydrophilic (polyglycerol caprylate) linkers in combination with a nonvolatile and mineral oil solvent with food additive status. The HLD parameters for lecithin, linkers, and oils were used to determine the lecithin-linker formulas that yielded HLD ∼0 (the surfactant phase inversion point), reaching interfacial tensions of 10 −2 mN/m, and high emulsification effectiveness with diluted bitumen. This effectiveness was close to that obtained with a simulated dispersant, and superior to the lecithin-Tween ® 80-ethanol formula. The lecithin-linker system produced 4–11 μm emulsified drops, sufficiently small to enhance the biodegradability of the dispersion.

          Kurzfassung

          Die Verwendung von Dispergiermitteln in großem Maßstab während der BP–Horizon-Öl-Katastrophe zeigte verschiedene Risiken, die mit diesen Formulierungen verbunden waren, insbesondere die Verwendung von Lösungsmitteln mit flüchtigen organischen Verbindungen (VOC) im Zusammenhang mit Atemwegserkrankungen und der schlechten biologischen Abbaubarkeit von Tensiden. Frühere Versuche, diese Probleme zu lösen, bestanden in Formulierungen aus Lecithin und Polyethylenglykol-Sorbitanmonooleaten (Tween ® 80), die immer noch die Verwendung eines flüchtigen Lösungsmittels, Ethanol, erforderten. In dieser Arbeit wurde das HLD-System (Hydrophilic-Lipophilic Difference) verwendet, um eine Lecithinformulierung zu entwickeln, die lebensmitteltaugliche, lipophile (Glycerinmonooleat (GMO) – und Sorbitanmonooleat (Span ® 80)) und hydrophile (Polyglycerylcaprylat) Binder (Linker) in Kombination mit einem nichtflüchtigen und mineralölhaltigen, als Lebensmittelzusatzstoff zu verwendendes Lösungsmittel enthält. Die HLD-Parameter für Lecithin, dem Linker und die Öle wurden verwendet, um die Lecithin-Linker-Formulierungen zu ermitteln, die einen HLD∼0 (den Inversionspunkt der Tensidphase), eine Grenzflächenspannungen von 10 −2 mN/m und eine hohe Emulgierwirkung mit verdünntem Bitumen erreichten. Diese Wirksamkeit war fast so hoch wie die, die mit einem simulierten Dispergiermittel erzielt wurde, und war der der Lecithin-Tween ® 80-Ethanol-Formulierung überlegen. Die Tröpfchengröße im Lecithin-Linker-System betrug 4–11 μm. Die Tröpfen waren ausreichend klein, um die biologische Abbaubarkeit der Dispersion zu verbessern.

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          Most cited references42

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          Fate of dispersants associated with the deepwater horizon oil spill.

          Response actions to the Deepwater Horizon oil spill included the injection of ∼771,000 gallons (2,900,000 L) of chemical dispersant into the flow of oil near the seafloor. Prior to this incident, no deepwater applications of dispersant had been conducted, and thus no data exist on the environmental fate of dispersants in deepwater. We used ultrahigh resolution mass spectrometry and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to identify and quantify one key ingredient of the dispersant, the anionic surfactant DOSS (dioctyl sodium sulfosuccinate), in the Gulf of Mexico deepwater during active flow and again after flow had ceased. Here we show that DOSS was sequestered in deepwater hydrocarbon plumes at 1000-1200 m water depth and did not intermingle with surface dispersant applications. Further, its concentration distribution was consistent with conservative transport and dilution at depth and it persisted up to 300 km from the well, 64 days after deepwater dispersant applications ceased. We conclude that DOSS was selectively associated with the oil and gas phases in the deepwater plume, yet underwent negligible, or slow, rates of biodegradation in the affected waters. These results provide important constraints on accurate modeling of the deepwater plume and critical geochemical contexts for future toxicological studies.
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            Principles of emulsion formation

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              Use of Fenton reagent to improve organic chemical biodegradability.

              E Chamarro (2001)
              Fenton reagent has been used to test the degradation of different organic compounds (formic acid, phenol, 4-chlorophenol, 2,4-dichlorophenol and nitrobenzene) in aqueous solution. A stoichiometric coefficient for the Fenton reaction was found to be 0.5 mol of organic compound/mol of hydrogen peroxide, except for the formic acid where a value of approximately one was obtained (due to the direct formation of carbon dioxide). The treatment eliminates the toxic substances and increases the biodegradability of the treated water (measured as the ratio BOD5/COD). Biodegradability is attained when the initial compound is removed.
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                Author and article information

                Journal
                tsd
                Tenside Surfactants Detergents
                Carl Hanser Verlag
                0932-3414
                2195-8564
                16 September 2019
                : 56
                : 5
                : 417-428
                Author notes
                [] Correspondence address, Prof. Dr. Edgar Acosta, Department of chemical engineering and applied chemistry, 200 College Street Toronto, Ontario M5S 3E5, Canada, E-Mail: edgar.acosta@ 123456utoronto.ca

                Suryavarshini Sundar is a MASc candidate at the Department of Chemical Engineering and Applied Chemistry of the University of Toronto, under the supervision of Professors Ramachandran and Acosta. She received her Bachelor of Technology degree from the National Institute of Technology- Tiruchirappalli, in India. She is interested to work in the field of colloids, formulation engineering, soft particle hydrodynamics, and interfacial science.

                Mehdi Nouraei received his Ph.D. in 2018 in Chemical Engineering on the formulation of lecithin-based delivery systems for food and pharmaceutical applications. He is currently a part-time Research Assistant in the Laboratory of Colloids and Formulation Engineering at University of Toronto. Dr. Nouraei is also an entrepenuer in the area of drug delivery.

                Thomas (Tom) Latta is a Professional Engineer, retired from full time work, and currently a part time Research Assistant in the Laboratory of Colloids and Formulation Engineering at University of Toronto. Tom was a Principal Process Engineer for WorleyParsons/Advisian with 14 years of experience in engineering design and 24 years of experience in refinery operations. Tom received the Energy Engineer of the Year award for 2003 from the Ontario Ministry of Energy and the Arbor Award from the University of Toronto in 2017. Tom has expertise in MEG Recovery Unit (MRU) design and chemistry and has been involved in research and development projects in flow assurance as well as water management. Tom has worked on piloting solvent extraction of bitumen as well as optimizing operations for iron and copper ore mining facilities.

                Edgar J. Acosta received his B.Sc. in Chemical Engineering (Summa Cum Laude) from the Universidad del Zulia (Venezuela) in 1996, and his M.Sc. and Ph.D. in Chemical Engineering from the University of Oklahoma in 2000 and 2004, respectively. He is currently a Professor of the Department of Chemical Engineering and Applied Chemistry of the University of Toronto. Dr. Acosta received the Provost Dissertation Award from the University of Oklahoma (2005), the Akzo-Nobel “Ralph Potts” award (2002), and the AOCS S&D best paper award (2004, 2008 and 2012), the AOCS Young Scientist Award (2010), and the Syncrude Innovation Award (2012). Dr. Acosta has published over 90 research articles, 8 book chapters, 2 patent applications, and has been author or coauthor of over 160 presentations at international conferences. His research encompasses the area of colloids, complex fluids and formulation engineering.

                Article
                TS110643
                10.3139/113.110643
                1bc4365e-2ce5-4017-8d30-7e1c2e133e71
                © 2019, Carl Hanser Publisher, Munich
                History
                : 21 June 2019
                : 20 July 2019
                Page count
                References: 47, Pages: 12
                Categories
                Enhanced Oil Recovery and Oil-Spill Dispersants

                Chemistry,Pharmaceutical chemistry,Analytical chemistry,General chemistry
                Formulierung,bitumen,HLD,Dispergiermittel,Hydrophil-Lipophil-Differenz (HLD),Microemulsions,formulation,emulsification,Mikroemulsionen,dispersant,Emulgierung,Bitumen

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